CN100418913C - Transparent zirconium oxide - tantalum and/or tantalum oxide coating - Google Patents

Transparent zirconium oxide - tantalum and/or tantalum oxide coating Download PDF

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CN100418913C
CN100418913C CNB2004800029201A CN200480002920A CN100418913C CN 100418913 C CN100418913 C CN 100418913C CN B2004800029201 A CNB2004800029201 A CN B2004800029201A CN 200480002920 A CN200480002920 A CN 200480002920A CN 100418913 C CN100418913 C CN 100418913C
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coating
transparent
tantalum
stabilised
thermally
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CN1741970A (en
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A·里茨
M·费格尔
B·亨谢
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Koninklijke Philips NV
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Koninklijke Philips Electronics NV
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/218—V2O5, Nb2O5, Ta2O5
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/22—ZrO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/154—Deposition methods from the vapour phase by sputtering
    • C03C2218/155—Deposition methods from the vapour phase by sputtering by reactive sputtering

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Optical Filters (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

High temperature-resistant transparent coatings based on zirconium oxide, which have improved dispersion properties and a high refractive index, comprise zirconium oxide with at least one additive from the group consisting of tantalum and/or tantalum oxide, whereby the proportion of Ta atoms, in relation to the total number of metal atoms in the coating is in the range of 5 to 30%.

Description

Transparent zirconium oxide-tantalum and/or tantalum oxide coating
The present invention relates generally to have the transparent zirconium oxide coating of at least a additive, additive is selected from tantalum and/or tantalum oxide, thereby coating has the high-temperature stability of raising.
The invention particularly relates to based on the shallow layer of transparent zirconium oxide coating or the Clear coating of form of film, zirconia coating comprises the additive that is selected from tantalum and/or tantalum oxide thus.
On the known outer or internal surface that coating is coated to lamp such as projecting lamp, so as from transparent spectrum the selected light component in particular range of wavelengths of reflection optionally.In doing so, the geometrical shape according to the active principle and the bulb of coating can cover whole bulb.For example, commercially available halogen lamp is exactly this situation.In this halogen lamp, filament or wire are disposed in the glass bulb center, and optical interference film or transparent interference coatings system are applied on the outside surface of bulb.Transparent interference coatings system can see through the light in the visible-range, and infrared rays is reflected.The infrared rays that comprises in the light of filament emission is got back to filament by transparent interference coatings systematic reflection, causes the filament heating.This causes launching the ratio reduction of light middle infrared (Mid-IR) and the raising of luminous efficiency.
As the replacement scheme of the whole coatings of bulb, also can only apply a certain proportion of tube face.For example, bowl-shape reflector lamp is exactly this situation, and is particularly useful for high performance lamps.For projection purposes, high-intensity discharge (HID) lamp and especially very-high performance (UHP) lamp is preferred because of its transparent nature.Use for these, need concentrated as far as possible light source, thereby the arc that forms is no more than the length of about 0.5-2.5mm between electrode tip.In addition, need high as far as possible light intensity.Can obtain these performances well with the UHP lamp.These lamps comprise the mercury lamp head in the heavy wall quartz glass bulb, it is bonded again goes within the oval vitreum, so that point location is consistent with ellipsoidal focus in the plasma body of mercury lamp head.Ellipsoidal internal surface has the thin mirror coating of selectivity dielectric.The light that electric arc is sent out is by preferred interference reflector coating emission in bulb hemisphere.Therefore the result is that light from bulb can more effectively be used for projection system, thereby has opened up the possibility of further miniaturization simultaneously.
Because the great flexibility of spectral effects, so multilayer interference filter is through being usually used in Clear coating.This multilayer interference filter often comprises the lamination of the different dielectric material that at least two kinds of specific refractory poweres are different.The transmission of these spectral filters and echo area depend on the coat-thickness of the independent coating of the high refractive index of coating and low-index material.This spectral filter can comprise independent coating, as in very simple mirror coating, or a hundreds of coating, as in the traffic pilot of transparent communication.
In the design of this spectral filter lamination, the refractive index difference of material therefor is even more important.Usually, this refractive index difference is big more, the specified spectral target function of then easy more acquisition.For example, when refractive index difference was high, the quantity and the total thickness of design floating coat were lower, and this has favourable influence to production cost.
For the Clear coating on the lamp, especially for lamp with quartz bulb, owing to thermal expansivity mates with the lamp wall material almost ideally, and since the low-refraction of low refractive index coating, therefore common use SiO 2For high refractive index coating, can use various materials, for example TiO 2, Ta 2O 5And Nb 2O 5Use for high performance lamps,, just can not use these standard materials with high refractive index as the UHP lamp of under 1000 ℃ of temperature, working, and, because they do not have enough stability.
Except transparent aspect, also must consider mechanical aspects: for example, transformation mutually in temperature limit and the performances such as recrystallization behavior under the high temperature.Variation in transformation or the phase transformation can cause the inefficacy of relevant parts mutually, for example passes through the variation of specific refractory power and/or coat-thickness.
For this reason, when on high performance lamps, using, must between properties of transparency and stability of material, compromise.At high temperature stable and be applicable to that an example of the material of Clear coating is that zirconium white is ZrO 2This material has low relatively specific refractory power, n ≈ 2.2 when λ=550nm, but in surpassing 800 ℃ drawing process, show the sign of coating chromatic dispersion.
When in the projection system that radiative geometrical shape quality is had high request, using, this chromatic dispersion causes the system efficiency loss, because light owing to chromatic dispersion departs from its assigned direction, can not focus on the principal reflection mirror of lamp system in the projection system ingate again, promptly spectral filter spectrum degenerates.
Recognize a kind of special-purpose coat system from US6356020, its first coating is the low refractive index coating on base material.At least one high refractive index coating is made up of 3 high refractive index independence coatings again, and one can comprise Ta in the middle of it 2O 5ZrO 2But, in US6356020, both openly be not used to make definite crystalline structure of coat system, there is not the temperature of openly determining of carrying out yet.
An object of the present invention is to improve the properties of transparency of high temperature oxidation resisting zirconium coating.In doing so, especially should under the situation of not damaging thermostability, improve ZrO 2The dispersion property of coating and specific refractory power.
Find now,, then can obtain having the high refractive index zirconia coating of low chromatic dispersion character if in coating, mix a spot of tantalum or tantalum oxide.
In first kind of embodiment, the objective of the invention is transparent heat-staple coating, comprise zirconium white and at least a additive, additive is selected from tantalum and/or tantalum oxide, in its floating coat the Ta atom with respect in the coating (1) all the ratio of atoms metals in the scope of 5-30%.
Coating according to the present invention is preferably unbodied.
This coating according to the present invention can be used for applying means of illumination, as the lamp of the purpose that is suitable for throwing light on, especially in motor vehicle.
Clear coating according to the present invention comprises zirconium white, and comprises tantalum and/or tantalum oxide additive.Use this Ta additive of specified amount, with respect to the sum meter of atoms metal in the Clear coating, the atomic ratio below using:
0.05≤Ta/Me≤0.30
Wherein Me represents the sum of atoms metal in the Clear coating.According to the preferably transparent coating of the present invention atoms metal except that Zr and Ta not, the atomic relation below therefore using:
0.05≤Ta/(Zr+Ta)≤0.30
Wherein the symbol of element is represented the quantity of each atoms metal.
Another class preferably transparent coating according to the present invention only comprises the zirconium and the tantalum of oxidised form, preferred ZrO 2Or Ta 2O 5Therefore, for the Clear coating that comprises zirconium white and tantalum oxide, the Ta atom with respect to the ratio of atoms metal sum in the coating in the scope of 5-30%, preferred 10-25%, more preferably 15-20%.
The ratio of zirconium atom in the coating with respect to the overall proportion of atoms metal in the coating, is 70-95%, preferred 75-90%, more preferably 80-85%.
Selection is according to the zirconium ratio and the tantalum ratio of coating of the present invention, so that each ratio is formed the 100wt% maximum value, with respect to the gross weight meter of this coating.
Zirconium white is also referred to as ZrO in specification sheets 2, also can represent ZrO within the scope of the invention x, x=1.9-2.1 wherein.
Tantalum oxide is also referred to as Ta in specification sheets 2O 5, also can represent Ta within the scope of the invention 2O x, x=4.9-5.1 wherein.
Can especially sputter on the substrate surface of wanting coated in regulation oxygen partial pressure p deposit thermally stable transparent coating by chemical vapour deposition under 20-300 ℃ the depositing temperature by at least one titanium target that comprises zirconium white and tantalum and/or tantalum oxide, coating comprises zirconium white and at least a additive, and additive is selected from tantalum and/or tantalum oxide.
This also has heating should be no more than the advantage that 150 ℃ base material also can apply now.
Coating according to the present invention is placed on or is coated on the main body or in the main body, opened up for example provide have very high stability and with pure ZrO 2Coating main body that phase specific refractivity (or specific inductivity) improves or parts and therefore come effectively and the possibility that designs of cost savings, wherein main body such as lamp, glass, especially heat-proof glass, plastics, gas sensor, transparent interference filter, transparent filter system, especially heating lamp reverberator, the cool down lamp reverberator, laser mirror, the antireflection system, bandpass filter, edge spectral filter (edge filter), the main body of low emissivity glass (low-e glass) and/or electronic application is as electronic unit, lamp or parts in diffusion barrier (diffusion barrier) or capacitor element or the optical information technology.This advantage also is effective to not allowing carrying out any heat treated product or base material more than 150 ℃.
Coating according to the present invention is characterised in that and ZrO 2The phase specific refractivity improves, and has improved thermal behavior and lower chromatic dispersion.
Transparent oxide covering according to the present invention specific refractory power when wavelength X=550nm is n=2.1 to n=2.3, preferred n=2.13 to n=2.28, more preferably n=2.15 to n=2.25.According to the present invention, higher specific refractory power is most preferred.
Coating according to the present invention thermal treatment in 950 ℃ stove is preferred after 15 hours to keep transparent, and/or thermal treatment after 15 hours in 950 ℃ stove, when wavelength X=550nm, has the specific refractory power of n=2.1 to n=2.3, preferred n=2.13 to n=2.28, especially preferred n=2.15 to n=2.25.
Except as otherwise noted, all under 23 ℃ envrionment temperature, measure.
For coat-thickness is the coating of 400nm, oxide covering according to the present invention is the dispersion index of tempering after 15 hours in 950 ℃ stove, also use " iHaze " expression hereinafter, iHaze value with 5-25nm, the iHaze value of preferred 8-18nm, the more preferably iHaze value of 12-16nm, most preferably＜the iHaze value of 15nm.Best coating does not have chromatic dispersion, so iHaze=0nm.Therefore, most preferably 〉=the iHaze value of 0nm to 20nm.Other suitable iHaze value is 〉=1nm, 〉=10nm and 〉=15nm.Must emphasize that the iHaze value of alap 0nm-1nm is most preferred.
According to Clear coating of the present invention preferably not separately but be coated onto base material especially on the transparent substrate with other coating combination.In this manner, for example, can obtain Clear coating such as interference coatings system.This transparent interference coatings system is also referred to as interference coatings in this manual, is made up of at least two also stacked toward each other contacts or contact opposite each other and refraction coating or other coating that have different refractivity separately.
Design consideration preferably transparent interference coatings of the present invention system, be used to be reflected in 250-5, light in the transparent optical spectrum wavelength scope of 000nm, preferred 380-3,000nm, more preferably 350-2,500nm, even more preferably 400-2,000nm, especially 420-1,500nm makes the interference coatings system have at least one first coating and according to second coating of the present invention, second coating has the specific refractory power that is lower than the first coating specific refractory power, they are disposed on the base material, preferably on transparent substrate, can replace if desired.Other suitable reflected range is 800-2,500nm, and 820-2,450nm, 850-2400nm, especially preferable range from 1,000 to 1,900nm and from 1,050 to 1,800nm.
Second coating specific refractory power when λ=550nm is n=1.32 to n=2.0, preferred n=1.35 to n=1.80, most preferably n=1.44 to n=1.75.Other suitable n value is 1.36; 1.42; 1.46; 1.48 and 1.50.For example, for SiO 2Coating, specific refractory power can be n=1.45.
Therefore another purpose of the present invention is the transparent interference coatings system that is used for the light in the reflective transparent spectrum designated wavelength range, coating has first coating, be lower than second coating of the first coating specific refractory power with specific refractory power, they are alternately arranged on transparent substrate, first coating mainly comprises zirconium white, and comprise at least a additive, additive is selected from tantalum and/or tantalum oxide, the Ta atom with respect to the ratio of atoms metal sum in the coating in the scope of 5-30%.
Therefore, transparent interference coatings according to the present invention has according to Clear coating of the present invention and at least one and has the other coating of low-refraction.Being similar to above-mentioned embodiment, also is preferred according to coating of the present invention, and promptly wherein first coating comprises zirconium white and tantalum oxide, the Ta atom with respect to the ratio of atoms metal sum in the coating in the scope of 5-30%, preferred 10-25%, more preferably 15-20%.More preferred features according to transparent interference coatings of the present invention can be inferred from the above-mentioned disclosure of preferably transparent coating, and are therefore needless to say more here.
Coating with high refractive index can comprise at least a compound and form agent as its glass, and wherein compound is selected from phosphorus compound and boron compound.
The conduct of preferred use silicon-dioxide is according to the low refractive index coating in the transparent interference coatings of the present invention.This coating also can comprise at least a compound and form agent as its glass, and wherein compound is selected from phosphorus compound and boron compound.
The thickness of high or low refractive index coating can change in wide scope, and for example can be between 500nm and 3 μ m.Separately the typical coating thickness of coating 20 and 500nm between, through be everlasting 10 and 200nm between.
Can comprise minimum two coatings according to transparent interference coatings of the present invention system, but it also can be by multiple successively high and low refractive index coating constitute.Can have a series of among the present invention up to the individual coating of hundreds of.
Thickness according to interference coatings of the present invention system can change in wide scope equally, and for example can be between 500nm and 3 μ m.According to the present invention, the suitable typical coating thickness of interference coatings system is between 50nm and 15 μ m, preferably between 75nm and 1.5 μ m, through being everlasting between 100nm and the 1 μ m.
According to the present invention, especially suitable coating compounds thickness is between 50nm and 20 μ m, preferably between 75 and 8 μ m, through being everlasting between 100nm and the 4 μ m, also through being everlasting between 300nm and the 3 μ m.
These and other aspect of the present invention is apparent from the embodiment of hereinafter describing, and illustrates with reference to it.
In the accompanying drawings:
Fig. 1 has shown the side view of section according to transparent interference coatings of the present invention system.
As shown in Figure 1, transparent interference coat system 3 comprises the coating 1 with high index of refraction, and its main component is zirconia (ZrO2) and have the coating 2 of low-refraction, its main component is silica (SiO2). First coating 1 with high index of refraction is formed on and can sees through base material 4 Outer surface on; 2 of coatings with low-refraction are formed on this coating. Replace then shape Become to have the more overbrushing layer 1,2 of high and low-refraction, thereby form the coating with requirement 1,2 stacked arrangement.
Can namely form according to transparent interference of the present invention on two surfaces at the surfaces externally and internally of bulb Coat system is so that reflected infrared ray and permission are by the light in the transparent spectrum visible-range Line.
Another purpose of the present invention is the lamp that comprises according to transparent interference coat system of the present invention. This lamp according to the present invention comprises translucent bulb, is arranged in the bulb for alight The silk and according to transparent interference coat system of the present invention, transparent interference coat system is arranged on lamp On the interior and/or outside of bubble, with reflected infrared ray with allow by the light in the visible-range.
Can for example be designed to halogen lamp according to this lamp of the present invention, or the silver-plated lamp in top, or excellent Select high performance lamps, for example high-intensity discharge (HID) lamp and especially very-high performance (UHP) Lamp. UHP lamp according to the present invention is especially preferred.
Can according to the whole bag of tricks base material form have at least a additive according to the present invention Zirconia coating, wherein additive is selected from tantalum and/or tantalum oxide.
The appropriate method of producing shallow layer can roughly be divided into four classes: physical vapour deposition (PVD) (PVD) Method, chemical vapour deposition (CVD) (CVD), plating and spraying method. Spraying method can be suitable for Thick coating is because they have the very high speed of growth. CVD and plating are usually not too suitable In forming oxide covering. Plasma excitation chemical vapour deposition (CVD) (PICVD) or suitable.
According to the present invention, spendable chemical gaseous phase depositing process have physical vapour deposition (PVD) as PVD, reactive magnetron sputter, ion sputtering, ion or plasma-enhanced deposition, plasma Excitation chemical vapour deposition (CVD) (PICVD) and other sputtering method well known by persons skilled in the art.
The PVD method can be divided into again three kinds of technology: deposition technique, sputtering method and laser ablation side Method (PLD).
Wherein, sputtering method is particularly suitable for oxide covering, and is preferred therefore.
Term " sputter " expression utilizes the cathodic metal spraying plating of ion, or in meaning widely On represent that also the sputtering sedimentation depositing materials is to base material.
In the simplest embodiment of sputtering method, diode apparatus be positioned at have positively charged Anode and the internal tank of electronegative negative electrode. Several mbar press evacuated vellel until only have The residual gas of power. The residual gas that uses is preferably inert gas (being generally argon gas), with Prevent the reaction with target or base material. Apply between anode and the negative electrode 150 and 3,000V between Voltage. Electronics accelerates towards anode, collides and make their ionization with the ar atmo that runs on the road. Ionized positively charged ar atmo accelerates towards negative electrode then, and from negative electrode or be positioned at negative electrode The target at top evicts out of atom. Except the neutral atom of target, also discharge secondary electron, its Make other ar atmo ionization. Therefore, under suitable condition, between two electrodes, just produce The plasma of stable state. The neutral atom of launching from target be distributed evenly at whole indoor and Produce shallow layer on the base material.
The kinetic energy of the sputter gas atom of neutral target atom and ionization 1 and 300eV between. With The kinetic energy of evaporation technique Atom is that about 0.1eV compares, and this is very high. Especially exist This kinetic energy Billy of the ion that is accelerated more is conducive to more closely with method of evaporating and in Smooth coating.
This general sputtering method is improved in many aspects. Replace simple diode Device, triode or RF diode also can be used for plasma and produce. For magnetron sputtering, magnetic Applying of field improved ionization probability and sputtering rate.
For the DC magnetron sputtering method, the diode voltage except about 1kV also applies Magnetic field. Produce magnetic field by the toroidal magnet around the target edge and middle central magnet, and The intensity that has hundreds of tesla on the target surface.
Magnetic field remains on the secondary electron that produces near the target. This has improved the electron-atom ionization The probability of collision, and also therefore improved near the plasma density of target. This is than conventional sputter side Method provides two big advantages: at first, sputtering rate improves, and secondly, plasma needs Low pressurized firing. Higher sputtering rate is extremely important to industrial production, in order to guarantee shorter Production time. And lower sputtering pressure also helps shallow layer. Because pressure is lower, Therefore have exogenous impurity gas atom still less, thereby the coating of sputter is purer.
Partial pressure of oxygen is set in p＜200mPa. According to the present invention, suitable partial pressure of oxygen can be 10 Hes Between the 100mPa, especially preferably＜80mPa. According to the present invention, other suitable partial pressure of oxygen exists 5 and 150mPa between, and 10 and 80mPa between, especially preferably 20 and 60mPa Between.
Another purpose of the present invention is to use the sputtering technology manufacturing to have the oxygen of at least a additive Change the method for zirconium clear coat, wherein additive is selected from tantalum and/or tantalum oxide, wherein zirconium and/or oxygen Changing the zirconium target uses with the target that comprises tantalum and/or tantalum oxide simultaneously. Perhaps, also can be from comprising zirconium With the alloys target of tantalum or comprise zirconia and the ceramic composite target of tantalum oxide produces coating.
The method according to this invention preferably uses argon gas to carry out as residual gas, and is whereby preferred Method is namely carried out in the presence of oxygen with so-called oxide mode. Herein, preferred method spy Levy be the method be 5 and 150mPa between partial pressure of oxygen under carry out, preferably 10 and 80 Between the mPa, especially 20 and 60mPa between.
A special benefits of the method according to this invention is to select low operating temperature. Cause This is characterised in that according to the preferred method of the present invention the method is the base between 20 and 300 ℃ Carry out under the material temperature, preferably between 100 and 280 ℃, especially between 150 and 270 ℃, Most preferably between 200 and 250 ℃. Also can change base material temperature according to each base material herein. Therefore, for the quartz glass base material, temperature between 250 and 280 ℃, preferred about 170 ℃, Be proved to be favourable, and silicon substrate is preferably coated between 100 and 250 ℃.
For example need not heat also and can obtain according to coating performance of the present invention and temperature stability. Especially Therefore its preferred temperature range also is 50-150 ℃.
Utilize the method according to this invention, even at low temperatures, also can produce with the transparent quality of height With good machinery and heat endurance be the mixed oxide of characteristics.
The method according to this invention provides than conventional ZrO2Low and high being coated with of refractive index of coating dispersivity Layer. In addition, with the ZrO that do not mix2About 800 ℃ compare, up to about 950 ℃ the time still Temperature stability and the transparency of coating have been significantly improved.
The method according to this invention also provides very smooth being coated with take the transparent quality of height as characteristics Layer. Refractive index according to coating of the present invention is between n=2.2 and the n=2.3 at λ=550nm, Relevant with Ta content.
The preferred variant of the method according to this invention is used the magnetron sputtering technology, again preferred two magnetic The keyholed back plate sputtering method. The field intensity of preferred magnetron or dual magnetron sputtering method is 10 and about Between the 200mT.
No matter use magnetron or dual magnetron method, the pulse mutation of method is preferred. Herein, for example, such method according to the present invention is preferred, and namely the method is 10 Hes Carry out under the pulse frequency between the 100kHz, preferably 20 and 70kHz between, especially 30 And between the 50kHz.
In order to obtain preferred thermally-stabilised coating, sputter density is 9 and 15W/cm2Between, especially preferably 11 and 12W/cm2Between. Sputter density can be at 1W/cm2And 40W/cm2It Between.
Sputter density is defined as the induction process power that normalizes to used target area.
Other possibility of the coating layer thickness that change applies according to the present invention is to adjust to be applied to each The power of Zr or Ta target. Herein, the method according to this invention preferably is applied to the total work of target Rate P=PThe zirconium target+P The tantalum target2,000 and 10,000W between, preferably 3,000 and 6,000W it Between, especially 3,500 and 5,000W between.
According to the present invention, the sputter mixed oxide coatings is possible, and is for example different by 2 kinds Metallic target or by one or more metal alloy targets with by the ceramic oxide target.
Operation is carried out in oxygen/argon atmospher usually.
Illustrate the present invention by following non-limiting embodiments.
Embodiment:
Use bipolar pulse dual magnetron sputtering method being of a size of the Clear coating that produces on the silica glass base material of 50 * 50mm according to zirconium white of the present invention and tantalum oxide.
For this reason, in oxide mode with the pulse-repetition of 40kHz corrode simultaneously by zirconium or tantalum make and along the limit each other in two metal magnetron targets of 20 ° of layouts, oxygen partial pressure is 40mPa, stagnation pressure 190 and 270mPa between.The cycle of each target is 25 μ s.Because be arranged in the heating unit behind the base material, the temperature when process begins on the base material is 270 ℃.The horizontal component that is applied to magnetron magnetic field over there at the substrate location place is about 30mT.
Zirconium and tantalum components in proportions change in the adjustable respectively power on being applied to two targets, and total power P (P=P The zirconium target+ P The tantalum target) 4kW always.
Utilization is according to this method of the present invention, and can obtain coat-thickness is the transparent oxide covering of 400nm.The ratio of Ta/ (Zr+Ta) is 0.11, and the specific refractory power at λ=550nm place is n=2.26.
According to the following statement of facts of the thermostability of coating of the present invention, promptly the specific refractory power of λ=n=2.26 of 550nm place can not change in up to 950 ℃ temperature range at depositing temperature.
The measuring condition leader:
T=23 ℃ (envrionment temperature)
Barometric point=laboratory air (normal pressure)
Drawing process
Under normal pressure in the laboratory air tempering.Tempering time: be 15 hours in all cases.
The X-ray diffraction method of masurement
In order to know phase composite and grain size, on Siemens D5000 diffractometer, carry out X-ray diffraction and measure.In (θ-2 θ) method, use the Bragg-Brentano geometry that does not have monochromator herein.The Ni spectral filter is got rid of incident Cu-K βLine.
Use Cu-K αPipe is as source of radiation.Typical measuring parameter is: step-length (Step logstep): 2 θ=0.02 °, integral time: Δ t=1s.For the beam current of 30mA, the acceleration voltage that uses is 40kV.
For distributing mutually, use Siemens develops and is integrated into the routine package in the Survey Software.
Mist degree (Haze)
The quantification of sample chromatic dispersion level is based on the mensuration of the parameter that is called " mist degree ".Utilize this measuring method, use the spectral luminosity survey meter measure transmission electromagnetic radiation the diffusion dispersive component and it is normalized to total transmission current (T Always=T Minute surface+ T Diffusion).Therefore mist degree in the transmission is defined within the value scope between 0 and 1,
It should be noted that it can not fully be compensated owing to normalization method because interference effect is measured curve and comprised current-modulation usually.But, owing in wide spectral range, measure, so their influence is farthest suppressed.
Utilize suitable mathematical method, can quantize sample chromatic dispersion level separately from spectrum measuring data.In present utilization, for this reason and according to equation (2), the integration visible spectrum range (area under a curve (" iHaze ") among the λ=380...800nm), thus make the current-modulation equalization.Because the coat-thickness of all samples is set in about 400 ± 10nm, can need not to consider any density effect of chromatic dispersion.Glass baseplate is owing to the chromatic dispersion contribution that the incomplete cleaning of any ununiformity or surface causes also can be left in the basket in this assessment, because it is in the order of magnitude scope of measuring accuracy.As the result of zero dimension " Haze " variable spectrum integral, " iHaze " variable that obtains has dimension [length is unit with nm].
iHaze = ∫ 380 nm 800 nm Haze ( λ ) dλ - - - ( 2 )
Following table has provided pure ZrO under all temps 2With according to the iHaze value of Clear coating of the present invention (base material that does not have coating: iHaze=2nm):
Figure C20048000292000142
Last table explanation, coating according to the present invention has the dispersion that significantly improves.
Surveying instrument: measuring in the spectral range of non-polarized light on the Cary5E of the Varian spectral luminosity survey meter at 350-800nm.In order to measure diffused transmission component T Diffusion(λ), provide integrating sphere (measurement point size: 10 * 10mm).
Herein, for vertical radiation incident, the orientation of the electromagnetic radiation of transmission and non-diffusion component derive from the measurement ball and focus in the beam dump.Diffusion signal component T Diffusion(λ) in the ball that scribbles PTFE (tetrafluoroethylene) (diameter 110mm), be hunted down, and measure by the protected photorectifier of direct irradiation that is not subjected to.It is high more, and then sample diffusion light is strong more.Because light is in multiple reflection on the ball internal surface at each point of sphere volume, therefore there is the yield of radiation of same wave long correlation.Because high light, detector not energy measurement from sample or from any direct signal on indirect illuminated ball surface (under the situation of airtight beam dump).If cover beam dump with the barium sulfate plate, then except diffusion component, specular component T Minute surface(λ) be also contained in the measurement signal.Calculate Haze according to equation 1.
The ellipsometric measurement method
For determining the specific refractory power and the coat-thickness of sample, use the ellipsometric measurement method to measure.The variation of polarization state when this method is reflected on the sample surfaces of research based on ripple.The variation of polarization state is described with the merchant ρ of two compound Fresnel reflection coefficient rp and rs.Equation below this is available is represented:
ρ = r ρ r s = tan ψ · θ 1 Δ
It is also referred to as the ellipsometric measurement fundamental equation.Herein, ψ representative amplitude ratio vertical and parallel component changes, and Δ tolerance is because the variation that differs between two partial waves (part-waves) that reflection causes.Subscript s and p represent perpendicular to be parallel to the partial wave that the incident horizontal plane is polarized.According to R.M.A.Azzam, N.M.Bashara, Ellipsometry and polarized light, NorthHolland, Amsterdam (1987) carries out the mensuration of specific refractory power.
If be that coating/substrate system limits suitable material model now, wherein its character (transparent constant, coat-thickness) combines with complex reflection coefficient and measuring parameter (wavelength, input angle), and then the variation of polarization state allows a series of important thin film parameters are made accurate elaboration.Use canonical parameter Lorentz oscillator model to describe the deviation of the transparent constant of sample.This has defined the vibration behavior of electronics when exciting with electromagnetic radiation that have with the flexible bonding of solid-state atom (referring to A.
Figure C20048000292000152
, Infrared Spectroscopic Ellipsometry, Akademie-Verlag, Berlin (1990)).Refractive index n that provides or n 550Relevant with wavelength X=550nm, and be accurate to ± 0.01 in.
For ellipsometric measurement, the outer ellipsometer SE800 of the spectrophotometric original position of SENTECH Instruments is suitable for, and it is with so-called polarizer-loop expansion pipe-sample-stepping-scanning-analyser (PCSSA) work in combination.
Estimate in the spectral range of 380-850nm, input angle changes between 55 and 75 ° (Δ=5 °).In order to make take off data be suitable for model, use the commercially available evaluating software routine package that is called AdvancedFit of SENTECH Instruments, it combines numerical method according to simplex algorithm.
Reference list:
1. Clear coating (first coating)
2. the second low coating of the refractive index ratio first coating specific refractory power
3. transparent interference coatings system
4. can see through base material

Claims (11)

1. transparent thermally-stabilised coating, comprise zirconium white and at least a additive that is selected from tantalum and/or tantalum oxide, be characterised in that comprise zirconic coating under 20-300 ℃ the depositing temperature by at least one target by vapour deposition in oxygen partial pressure p＜200mPa deposit to wanting on the coated substrate surface, wherein this target selected among zirconium, zirconium white, tantalum and/or tantalum oxide, thereby in the scope of 5-30%, the refractive index value of coating is n=2.1 to n=2.3 to the Ta atom during and λ=550nm with respect to the ratio of the middle atoms metal sum of coating (1) in the coating.
2. transparent thermally-stabilised coating as claimed in claim 1 is characterised in that this coating based on zirconium white and tantalum oxide, and wherein the Ta atom is 10-25% with respect to the ratio of the middle atoms metal sum of coating (1).
3. transparent thermally-stabilised coating as claimed in claim 1 is characterised in that the thermal treatment after 15 hours in 950 ℃ stove of this coating, keep transparent and/or when wavelength X=550nm specific refractory power be n=2.1 to n=2.3.
4. transparent thermally-stabilised coating as claimed in claim 1 is characterised in that coat-thickness is that this coating thermal treatment in 950 ℃ stove of 400nm kept the iHaze value 〉=0nm to 25nm of transparent and/or this coating after 15 hours.
5. transparent thermally-stabilised coating as claimed in claim 1 is characterised in that coating is unbodied.
6. transparent interference coatings system, being used for reflective transparent spectrum particular range of wavelengths is 250-5, the light of 000nm, its floating coat (3) comprises one or several first coating (1) and one or several second coating (2), second coating (2) has than the low specific refractory power of first coating (1), they are arranged alternately on the base material (4), are characterised in that described one or several first coating (1) such formation as claimed in claim 1.
7. transparent interference coatings as claimed in claim 6 system is characterised in that second coating (2) specific refractory power when wavelength X=550nm is n=1.32 to n=2.0.
8. lamp, have as any described transparent thermally-stabilised coating in the claim 1 to 7 and/or transparent interference coatings system, be characterised in that thermally-stabilised coating that this is transparent and/or transparent interference coatings system are arranged on the interior and/or outside of bulb and/or wherein.
9. be used to apply the application of main body as any described transparent thermally-stabilised coating in the claim 1 to 5, be characterised in that this main body is selected from pack equipment, divide beam device, the optical fiber parts, means of illumination, gas sensor, glass, plastics, transparent element, spectral filter, lens, mirror, transparent filter system, antireflection system, and/or the main body of electronic application.
10. transparent thermally-stabilised coating as claimed in claim 9 is used to apply the application of main body, is characterised in that this main body is selected from lamp, lampshade, heat-proof glass, low emissivity glass, laser mirror, heat mirror, Cold Mirrors, bandpass filter, edge spectral filter, diffusion barrier and/or capacitor element.
11. the method for any described transparent thermally-stabilised coating in manufacturing such as the claim 1 to 5, this transparent thermally-stabilised coating comprises zirconium white and at least a additive that is selected from tantalum and/or tantalum oxide, be characterised in that will comprise by vapour deposition by at least one target under 20-300 ℃ the depositing temperature zirconic coating in oxygen partial pressure p＜200mPa deposit to wanting on the coated substrate surface, wherein this target selected among zirconium, zirconium white, tantalum and/or tantalum oxide.
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